Leo D. Brown and James A. Ibers
2188 Inorganic Chemistry, Vol. 15, No. 11, 1976 (8) W. R. Busing and H. A. Levy, J . Chem. Phys., 26, 563 (1957). (9) A. J. C. Wilson, Nuture (London), 150, 152 (1942). ( I O ) H. P. Hanson, F. Herman, J. D. Lea, and S. Skillman, Acta Crystuliogr., 17, 1040 (1964). (11) R. F. Stewart, E. R.Davidson, and W. T. Simpson, J . Chem. Phys., 42, 3175 (1965). (12) D. T. Cromer and D. Liberman, J . Chem. Phys., 53, 1891 (1970). ( i 3 j Supplementary material. (14) J. M. Stewart, “X-RAY 67”, Technical Report 67-58, Computer Scicnce Center. University of Marvland, 1967. (15) W. R; Busing, K. 0. Ma&, and H. A. Levy. “ORFLS”, Report ORNL-TM-305, Oak Ridge National Laboratory, Oak Ridge, Tenn., 1962. (16) M. E. Pippy and F. R. Ahmed, “KRC Crystallographic Programs”, National Research Council, Ottawa, 1968.
(17) C. K. Johnson, “ORTEP”, Report ORNL-3794, Oak Ridge National Laboratory, Oak Ridge, Tenn., 1965. (18) T. J. Kistenmacher and D. J. Szalda, Acta Crystallogr., Sect. B, 31, 1659 (1975). (19) T. J. Kistenmacher, T. Sorrell, and L. G. Marzilli, Inorg. Chem., 14, 2479 (1975). (20) T. J. Kistenmacher,L. G. Marzilli, and D. J. Szalda, Acta Crystallogr., Sect. 8,32, 186 (1976). (21) E. Sletten and N. Flogstad, Acta Crystallogr., Sect. B, 32, 461 (1976). (22) T. Sorrell, L. G. Marzilli, and T. J. Kistenmacher, J . Am. Chem. Soc., 98, 2181 (1976). (23) D. J. Szalda, T. J. Kistenmacher, and L. G. Marzilli, to be submitted
for publication. (24) D. W. Martin and T. N. Waters, J . Chem. Sot., Dalton Trans., 2440 (1973).
Contribution from the Department of Chemistry, Northwestern University, Evanston, Illinois 60201
Structural Studies of Triazenido Complexes. 1. Crystal and Molecular Structure of trans-Bis (triphenylphosphine) carbonyl( 1,3-di-p-tolyltriazenido) hydridoruthenium(I1) , trans- [Ru(H)( C H 3 C 6 H 4 N 3 C 6 H 4 C H 3 ) (co)( P ( C 6 H 5 ) 3 ) 2 ] LEO D. BROWN and J A M E S A. IBERS* Received May 19, 1976
AIC60366U
The structure of trans-bis(triphenylphosphine)carbonyl( 1,3-di-p-tolyItriazenido) hydridoruthenium(I1) has been determined from three-dimensjonal x-ray diffraction data collected by counter methods. The compound crystallizes in the triclinic space group Cil-P1 with two molecules in the unit cell of dimensions a = 14.074 (2) A, b = 15.264 (3) A, c = 12.195 (2) A, a = 109.78 (l)’, /3 = 111.74 (l)’, y = 65.03 (l)’, and V = 2154 A3;pcalcd = 1.35 and pobsd = 1.34 g ~ m - A ~ .full-matrix least-squares refinement of the structure by standard procedures resulted in an R index of 0.038 for the 5847 independent data for which Fo2 > 3a(F02). The coordination about the ruthenium atom is approximately octahedral. The triazenido ligand is coordinated to the metal atom in a bidentate mode with a N ( 1)-Ru-N(3) angle of 57.7 (1)’ and a N ( l)-N(2)-N(3) angle of 105.2 (3)’. The Ru-N(3) bond length is 2.179 (3) A compared with the Ru-N(l) distance of 2.149 (3) A. The N-N bond lengths within the triazenido moiety are equal with N(l)-N(2) and N(2)-N(3) distances of 1.318 (4) and 1.310 (4) A, respectively. The entire ruthenium-triazenido system is essentially planar, indicative of ?r delocalization over the whole system.
Introduction The study of transition metal complexes containing triazenido ligands has increased greatly in the last few years. Although isoelectronic with allyl (I), carboxylato (II), and R
Table I. Crystal Data for trans.[Ru(H)(dtt)(CO)(PPh,), ] Mol formula Mol wt Cell constantsa
R
I
I1
111
IV
amidino (111), the triazenido ligand (IV) had not received much interest compared with the former ligands. Owing to the fact that each of these anions is potentially either a twoor four-electron donor, much research has centered on the preferred bonding arrangement of the ligand in a given system. As early as 1941, Dwyer and Mellor’ proposed that 1,3diphenyltriazenido (dpt) complexes of nickel contained bidentate triazenido ligands, resulting in a strained fourmembered chelate ring. This formulation was later disputed2 and ultimately shown to be incorrect. Structural studies of [ N i ( d ~ t ) 2 1 2 ,[Cu(dpt)zl ~,~ 2,4 [Pd(d~t)212,~ and [Cu(dpt>1z5 confirmed that the triazenide ligand actually bridges the metal centers in these compounds. The first compound to be shown to have a bidentate triazenide coordinated to a single metal atom was Co(dpt)3.6 The structures of two different crystalline forms have been reported (the first with toluene s ~ l v a t eand ~,~ the other unsolvateds), and both confirm the presence of the
Space group Z Density Crystal dimensions Crystal vol Absorption coeff, pa a
C ,,H, jN30P2Ru 878.96 amu a = 14.074 (2) A b = 15.264 (3) A c = 12.195 (2) A a = 109.78 (1)” p = 111.74 (1)” r = 6 5 . 0 3 (1)“ V = 2154 A’ ci p i 2 1.35 (calcd), 1.34 (exptl) g cm-’ 0.521 X 0.452 X 0.173 mm 1.16 x l o T 2mm3 40.29 cm-’
-
Cu K a , ( h 1.540 562 A) at 22 “ C ambient temperature.
four-membered M-N-N-N ring. Very recently, synthetic work has been reported on organometalliccomplexes of secondand third-row transition metals containing triazenido liga n d ~ . ~ -These ’ ~ workers have deduced both bridging and bidentate bonding modes for the triazenido ligand in these complexes. We present here the structure of one such complex, trans-Ru(H) (dtt) (CO) (PPh3)29a (dtt = 1,3-di-p-tolyltriazenido, Ph = C6H5) in which the dtt ligand is coordinated to the metal in a bidentate fashion.18
Triazenido Complexes
Inorganic Chemistry, Vol. 15, No. 11, I976 2789
Figure 1. Stereoscopic drawing of the unit cell of trans-[Ru(H)(dtt)(CO)(PPh,),l. The x axis is perpendicular to the plane of the paper going away from the reader; t h e y axis is vertical, and the z axis is horizontal and to the right. For the sake of clarity the hydrogen atoms have been assigned an arbitrarily small thermal motion of 1 A'. The thermal ellipsoids are drawn at the 20% probability level.
Experimental Section Orange crystals of truns-Ru(H)(dtt)(CO)(PPh3)2were obtained by recrystallization from a benzene-methanol solution of material kindly supplied by Dr. S. D. Robinson. An examination of the crystals by precession methods established- that they belong to the triclinic system. The space group is C,'-Pl, as ultimately confirmed by the structure solution. The crystal used for intensity measurements was mounted on a glass fiber approximately along the crystallographic b axis. The 12 faces of the-crystal were identified as belonging to (OOl}, { l l O ) , ( l l i ) ,(Oll},(101), and (OlO}. The lattice constants were determined by a least-squares analysis19 of the angle settings of 18 hand-centered reflections on a Picker FACS-I diffractometer (X(Cu K q ) 1.540562 A) in the range 55" > 20 > 45'. The refined, reduced cell constants and other relevant crystal data are given in Table I. Intensity data were measured in the 8-28 scan mode on the Picker FACS-I using Ni-filtered Cu K a radiation at a takeoff angle of 3.8". The counter was positioned 32 cm from the crystal with an aperture 4.3 mm high and 4.3 mm wide. The reflections were scanned a t 2"/min from 0.8O below the Ka1 peak to 0.8' above the Ka2 peak. Stationary-crystal, stationary-counter background counts of 10 s each were taken a t the beginning and end of each scan. Copper foil attenuators were automatically inserted if the counting rate approached 7000 counts/s. Intensity data for kh,-k,=kl were collected out to 20 = 120O. Past this point only about 5% of the data appeared to be above background. During the data collection the intensities of six standard reflections were measured after every 100 reflections. These standards showed no significant variations throughout the data collection. The intensity data were processed as described p r e v i o ~ s l ywith ~~ the parameter p chosen as 0.04. Of the 6664 unique data collected, 5847 independent reflections were found with significant intensity (Zo > 3g(Z0)) and were used in the subsequent solution and refinement of the structure. The ruthenium atom and both phosphorus atoms were located from a Patterson synthesis. A least-squares refinement20 of these three atoms followed by a difference Fourier synthesis located an additional fifteen atoms. The remainder of the nonhydrogen atoms were located in a subsequent difference Fourier map. In the full-matrix least-squares refinements, the function minimized is Cw(lFol - IFc1)2,where lFol and lFcl are the observed and calculated structure amplitudes and w = 4FO2/u2(Fo2). Atomic scattering factors and the anomalous dispersion terms were taken from the well-known sources.21 The carbon atoms of the eight phenyl rings in the structure were refined as rigid groups22initially with individual isotropic thermal parameters (&h symmetry, C C = 1.395 A). With all of the nonhydrogen atoms included with isotropic thermal parameters, the structure refined to R = 0.118 and R, = 0.171, where R = CllFol- lFc~l/EIFol and Rw = ( C W ( l F 0 l - IFcI)2/~wF02)1'2. Before proceeding any further an absorption correction was applied to the intensity data. The transmission factors ranged from 0.375 to 0.671 ( p = 40.3 cm-1 for Cu K a radiation). In the subsequent least-squares cycle the nongroup atoms were refined anisotropically. In the resulting Fourier map all of the phenyl and methyl hydrogen atoms were located. At the position of the hydrido ligand, however, two weak peaks were found that suggested a slight positional disorder
between the hydrido and carbonyl ligands. In the difference Fourier map the electron density of the peak closer to the ruthenium atom was greater (0.83 e A-3) than the further peak (0.66 e A-3). This observation is consistent with a significant contribution of the hydrido ligand to the nearer peak. In the next least-squares cycle the total occupancy of the carbonyl ligand was constrained23 to be 1.O between the two ligan&positions resulting in a 20% carbonyl for the two weak peaks (isotropic thermal motion) and an 80% carbonyl (anisotropic thermal motion) a t its established position. Owing to the significant electron density of the hydrido ligand when compared with that of the 20% carbonyl group and also because of the expectation that the Ru-H vector is near to but not necessarily coincident with the R u C ( 2 ) vector, no further embellishments of the model of disorder were deemed fruitful. All of the hydrogen atoms were included in the final calculations as a fixed contribution. The positions of the phenyl hydrogens were uniquely determined from the phenyl carbon positions assuming ideal geometry and a C-H distance of 0.95 A. The six methyl hydrogen atoms were ideally located by a least-squares fit based on the positions of the peaks found in the difference Fourier map. Each of the 44 hydrogen atoms was assigned an isotropic thermal parameter 1 A2 greater than the carbon atom to which it is attached. After an additional anisotropic least-squares cycle with the hydrogen contribution, agreement indices of R = 0.066 and R, = 0.101 were obtained. On the difference Fourier map virtually all of the significant residual peaks (average peak height -0.9 e A-3) were associated with the phenyl ring carbon atoms. Apparently some of the rings had significant librational motion not accounted for by the isotropic model. To remedy this problem the rigid-group atoms were allowed to refine with individual anisotropic thermal parameters.20 The final full-matrix refinement (5847 independent observation, 436 variables) resulted in R = 0.038 and R, = 0.060. The error in an observation of unit weight is 2.28 electrons. The largest peaks in the final difference Fourier synthesis were approximately 0.3 e k 3(equivalent to less than 1OOh of a carbon atom). Of the 577 unobserved reflections 13 were found to have IFo2 - Fc21 > 3u(FO2). It is important to note that inclusion of anisotropic thermal motion for the carbon atoms of the phenyl groups, while improving the agreement indices and lowering the estimated standard deviations with concomitant increase in computing time, did not result in any significant shifts in the atoms of the inner coordination sphere. We conclude, therefore, that use of this more elaborate model is not generally justified. The final positional and thermal parameters for the nonhydrogen atoms along with their estimated standard deviations are given in Table 11. Table 111 lists the positional and orientation parameters for the eight rigid groups. The root-mean-square amplitudes of vibration for the anisotropic atoms are given in Table IV.24 Table V gives the idealized positions of the hydrogen atoms.24 A listing of the observed and calculated structure amplitudes is also available.24
Description of the Structure and Discussion The crystal structure consists of discrete monomeric units of the ruthenium complex with no molecules of solvation. A stereoview of the contents of the triclinic unit cell is given in The geometry of the six-coordinate transFigure 1.
Leo D. Brown and James A. Ibers
2790 Inorganic Chemistry, Vol. 15, No. 11, 1976
Table 11. Positional and Thermal Parameters for the Nonhydrogen Atoms of trans-[Ru(H)(CH,C,H,N,C,H,CH,)(CO)(P(C,H
...**........ E .....*.*. ......*... A
&TOM
Y
.t
I.....
.........lf!,~~.~:~...?~~......, 8
1 1 . .
2
....*......
.... 033
012
**.*..*.
. . I . .
813
.**I.
j)3)2]
......
823
I I,....
0,3932~7123l
64.71 (251
49.781211
7 0 . 4 1 (29)
-28.011161
16.91 ( 1 8 )
6.51f161
0.285726167)
0.358331 (801
61.441661
50.32 156 I
7 1 -40 1 7 8 1
-25.521491
10.55157)
14.831 5 2 1
0.157648169)
0.450879183)
69.381701
51.L61561
73.40(801
-27.69151)
17. 991591
9.251531
0.090971241
0.252211721
0 . 2 3 2 8 9 f 281
65.11231
46.411 8 I
86,91291
-19.7117)
21.8121)
7.E119)
N12l
0 e 1 1 9 3 3 L 241
0.16694121)
0.15659127)
67.51231
48.21181
7 5 . 8 1261
-19.3117)
17.912CI
ll.6(19)
N13)
0.208191231
0.110981211
0.71969 1261
61.01221
49.1118)
7 5 . 0 126)
-19.51171
1 6 . 5 1 20)
15.6(iRI
c111
0.339761391
0.15412135)
0.505131431
74.2[371
58.51301
83.31431
-36.31261
16.61331
14.4130)
0111
0141672(301
0,113941 3 2 1
0.57264137)
75,11301
107.7(341
123.31431
-30.1126)
-21.1129)
70.11331
C12)
0.1702(151
0 . 3 3 5 4 114)
0.4687 1 171
0121
0.13741171
0.4151116)
0.54701201
C13)
-0.30633143)
0.54963144)
0.05701156)
62.2140)
103.2143)
244.21951
-1,1133 I
32.7 1 5 0 )
85.5 I 5 4 1
-0.00703(511
122.71471
61.7(301
150.71601
-14.6130 I
51,3144)
-1.5134) 17.0[241
RU
0.217394121)
O.216205(19)
Pill
0.320697173)
P12)
0.1165321771
N111
C14I
0.39257 1451
-0.29355135)
3.99(381 8 . 6 3 1541
PHlCl
-0.005921171
0.32441 ( 1 5 )
0.18573(231
62.R128l
50.3123 I
100.71381
-18.8 1 2 1I
24.2 1 2 6 1
PHlC2
-0.080901221
0.29977(16)
0.078I+5(231
82.61301
67.51281
107.11431
-13,71261
11.71311
9.91281
pH123
-0.178001211
0.37271123)
0.03713(231
87.9119)
99.2 140 I
110411471
-15.11321
0.8134)
33.31351
PHICL
-0.200121181
0.47029(191
0.10309(291
76.0133)
72. 9f 31)
178.11601
40.2t 371
56.41361
PHIC~
-0.12514123)
0.49494(13)
0 ,210381281
87.5~3~)
50.2125)
188.41621
-16.11251
45.1(401
27.6132)
PH1C6
-0.OZ8041701
or42~3o(ini
0 . 2 5 1 7 0 1 72)
66.71291
50.4(241
145.3(491
-19.0
23.2f30)
19.1(27)
DH2Cl
0.252471191
0.01273113)
0.15864119)
60.7126)
5 3 . 0 1221
74.11311
122) - 1 8 . 8 120)
22.21231
14.5121)
P H ~ C ~ 0.343151191
-0.049911161
0.22624(16)
6 8 . 7 129)
43.4(251
90.21 3 6 1
-24.11221
5.11261
15.7125)
PHZC3
0.388421171
-0.146971161
0.17263(231
bR, 9 I30I
59.1 126 I
122.8146)
-13.51231
16.4l301
23.91281
PHZC4
0.34302121)
-01185401131
0 05144123)
79.6L32l
55.61251
115.11451
-14.31231
40.0 1 3 1 )
14.5(27)
P H L C ~
0.25234(221
-0.12276(181
PH2C6
0.207071181
II 2 3 7 a
PH~CI
PH3C2
0.411221201 0 , 4 9 5 5 9 1231
PH3C3
-714196 I
100 9 (371
69.61 2 9 1
82.81371
-16.41771
27.61361
9.81271
0 . 0 3 7 4 4 1 19)
66.91321
5J.71251
66.3(321
-9.3(23)
15.81261
15.81231
0.33887(20)
0.49176 (191
67.2127)
51.5(221
-2n.zizii
-2.4f24l
23.1(271
0.355111231
0.47673172)
9 0 . 0 1151
86.5132)
120.51481
-51.7 1 2 9 )
13.8132)
13.91321
0~561031711
0.401271751
0.57543130)
95.7 1391
99.51391
170.21641
-66.2(331
-6.5 I391
24.2140)
PHJCI,
0.5420'31251
0.431191251
0.68917124)
116.71431
93.91301
133.81531
-67.1135)
-23,81381
32.21361
PH3C5
0.457701291
0.41495127l
0 lOirZl(l8I
180.3 I601
133.9147)
79.91391
-99.81461
-17-4(38)
29.0134)
PPi3:b
0 . 3 9 2 2 7 1 221
0.368781221
0.605501221
116,31411
100.21361
84.0(381
-68.0 133)
-3.0 1 3 1 I
20.31301
PH4Cl
0.416691191
0.2C0631171
0,26769(23)
61.9126)
61.31241
89.71351
-27.7 f 2 1 )
17.+1241
14.E124l
PH4C2
0 . 4 7 8 2 4 (241
0.lC8431191
0 , 2 9 7 4 2 124)
96.41361
6 0 . 11 26)
173.61461
- 2 2 - 6125 I
43.31341
1219128)
PH4C3
0.55362 (241
0.039391171
0.234O3(311
100.91421
71.91321
154.4158)
-16.11301
51071411
14. 2 1 3 5 1
PH4CL
0 , 5 6 7 4 4 1241
0.06255127)
0.140901291
93.51411
96.6139)
136.51561
-28.8 I 3 3 1
44.31401
-3.91371
PH4C5
0.505891?71
0.15476(261
0. l 1 1 1 7 ( 2 6 l
lOl~OI42l
135.11461
131,8152)
-23.21361
56.5 1 3 9 )
41. 11401
PH4C6
0.430511231
0.22390119)
0,17457127)
86.9 I 3 6 1
96.51351
128.71491
-22.41291
19.5(351
42.71351
PH5Cl
0.24102119)
8.390461151
0.283951201
59.7126)
56.71231
79.3132)
-24.3(?0 I
9.9123)
23. 2 ( 2 2 1
PH~CP
0.19294122)
0.373501161
0 .159621191
74.5 I l l )
80 * 1 1 291
8 0 . 0 1351
-28.6 I25 I
13.31261
P H ~ C ~ 0.128571231
0.453231231
0 . 1 0 3 3 6 11 8 )
96.1(361
115. 31421
97.51411
-29,61321
7.4(311
48. 3135)
PH5C4
- 0.
I1 7 I
-0.016161i6I
82.0 1341
21.31261
0.54991(191
0,171'+4(28)
88.9 1 3 R I
91. 8 1 3 6 1
169.01611
- 7 1 . 2 1 30 I
5.4(381
75.21411
P H ~ C ~ 0.16036124l
0.566661141
0,295781771
92.913~1
6 3 . 81291
154.41571
-26.3(271
4 4 . C1331
PH5C6
0.224731221
0.48714116)
0.35204(181
80.91321
6 0 . 4 1 26 I
113.31421
-31.5124)
4.it3r) *.?129)
PHbCi
-0.032211151
0.212231191
0.46807125)
72.9129)
75.2128)
74.21331
PHbC2
-0 a 0 7 6 7 0 1 2 3 1
0.31145flqI
0.40 042 ( 2 8 )
96.81351
93. n1 3 2 )
112.71441
PHbC3
-0.18932125)
0.357771201
0 . 3 6 9 1 8 1 311
98.81431
114.71431
139.91541
0.112281231
-26.9
I24 I
-10.9(271
22.71251
27.3(27) 15.21251
i2.5132)
23.3 ( 3 1 1
6.01351
54.91431
51.81401 54.0146)
PHSC~
-0.257451161
0.3G498(301
0.345561301
79.8139)
177.61591
119.5 ( 5 1 1
-16.4140)
33.91361
PHSC~
- 0 . 2 1 2 9 7 1 221
0.205661291
0.35322 1 30)
84.2 1 3 9 )
172.51571
1?3.C(53)
-65.7140 1
16.91361
30.8144)
PHbC6
-0e100351731
0.15934(191
0.38447 128)
8 2 $ 9( 3 4 I
115.21391
lC6.5(44)
-54. 61311
1 5 . 0 1 30 I
27.81331
11.9123)
PH7Cl
O . l L 3 4 1 I241
0.16588123l
0 . 6 1 29 7 1 1 7 )
90,913C)
57.71241
81.1135)
-25.0(231
17.11 2 6 )
PH7C2
0.21140 ( 2 6 1
0.216061231
0.700001241
156.91491
73.0130)
85.4139)
-62.4(331
22.51351
5.31271
PH7C3
0.233461301
0.21841126)
0.82712121)
213.1165)
95. G I 3 7 1
78.1(401
-87.6142)
2.91401
-1.7131)
PH7C4
0.187541321
0.17060128I
0 , 8 5 7 1 1 118)
183.11601
89.3136)
77.11 38)
-41.0
PH7C5
0.119551311
0a120421291
0 . 7 6 9 9 9 1 271
160. 1 1 5 9 I
175-5159)
104.61491
-93.61501
PH7C6
0.097461271
0.118061271
0.64786 ( 2 3 1
144.9 I 5 0 1
182.31551
99.11441
-112.41461
PH8Cl
0~143321241
0.02617(15)
0 . 3 8 8 4 2 1241
1 0 3 . 3 1361
57.71241
94.71371
PHBCZ
0.225431271
-0.04239124)
o .454n6
155.9 ( 5 2 )
56.61271
PH8C3
I 26)
(40)
19.5 1 3 8 )
9.61291
95.7143)
4 8 . 8 1451
1.01371
4 3 . 91401
-44.5 ( 2 5 1
43.2130)
162.1f631
-27.01321
62 I 4 ( 4 8 )
0.91241 25.01341
0.253601311
-0.143291201
0 . 4 0 2 11 1 42)
213.2178)
57.61331
268.110)
-16.81411
1 2 4 . 2 17 6 1
P H ~ C ~ 0.199661381
-0.175631171
0,28292(431
284.51921
71.5136)
308. 1111
-83.3 I 4 9 1
216.518111
-44.11491
PH8C5
0.11755134)
-0.iG707(271
0 . 7 1 6 L U 1281
220.7174)
115.01441
178.91641
122.1158)
- 6 9 . 11461
PH8C6
0.089381241
-0.OG6181741
0 . 2 6 9 2 11 241
134.6147)
92.51331
116.0(451
..
r
-117.51521 -69.2 I 3 4 1
61.51 3RI
34.91491
-27.9 I 3 7 1
..*....*.*.*.......****..**.~*..***.....*....*.**......**'*..~...~.**.....r*..1**..**......I
'ESTIMATED
STANOAQO OEWIATIONS I N THE LEAST S I G N I F I C L N T F I G U S E I S ) A9E G I V Z N I N PPFENTHESES I 4 T H I S 4 N O ALL SU0SE9UENT TA0LES.
FORM OF 1HE ANISOTROPIC
THERMAL E L L I P S O I D I S :
ARE THE THERMAL C O E F F I C I E N T S X lo4.
'THIS
2
2
2
EXPC- 1 B l l H t E 2 2 L ( t 0 3 3 L t Z B l 2 H K * 2 8 1 3 H L + Z E Z 3 U L I 1.
'THE
THE Q U A N T I T I E S G I V E N I N T H E TABLE
ATOM AND THCSE THAT FOLLOW &RE THE CARBON ATCHS OF THE ANISCTSOPIC R I G 1 0 GROUPS.
THE
P O S I T I O H P L PPRAMETEPS AN0 T H E I R ESTIMATED ST4NOhRD D E V I A T I O N S ARE DERIVED FRO* THE R I G I D GROUP PARAMETERS GIVEN I N TABLE 111.
among the six P-C distances.) The equatorial plane consists RuH(dtt)(CO)(PPh3)2 molecule (shown in Figure 2) is of the hydrido, carbonyl, and triazenido ligands. The angles approximately octahedral with the triazenido ligand coorbetween these ligands are very distorted from ideal octahedral dinated in a bidentate fashion. The two trans triphenylgeometry. This distortion is caused primarily by the small bite phosphine ligands show a P(l)-Ru-P(2) angle of 173.44 (3)'. of the triazenido moiety resulting in a N( 1)-Ru-N(3) angle The Ru-P(l) and Ru-P(2) distances of 2.343 (1) and 2.354 (1) A, respectively, are typical in such Ru(I1) c ~ m p l e x e s . ~ ~ , ~of~57.7 (1)'. A view of the inner coordination geometry about the ruthenium atom makes this fact clear (see Figure 3). A (The apparently significant difference in the two Ru-P distances may result from an underestimation of the standard listing of relevant bond distances and angles is given in Table deviations by a factor of 2 or 3 as judged by the agreement VI.
Inorganic Chemistry, Vol. 15, No. 11, 1976 2791
Triazenido Complexes
Table 111. RigidGroup Parameters of vans-[Ru(H)(CH3C,H,N3C,H,CH,)(CO)(P(C,H,),),]
.......**.
GROUP
A
E
z
I
X
DELTA
ETA
EPSILON
......~...*.....*........*.....*...***...*~..**.......*,**~....~..~...***.....*...........'..*r.......
pni
-0.103U21ljl
0.144~1118I
0 .l+?665 ( 1 6 )
0 . 3 9 7 3 5 1141 -0.086331 1 2 ) 0.33507115)
PH4
0.49207l151
0.111591151
PH5
0 , 1 7 6 5 5 1141
0.470in(i41
0.20430 1141 0.227701171 0,37682 I 1 7 1
pnz
a.zw751131
QH3
Pns ~
n
-0.14V83115l
0.165 47 I 1 3 I
7
-0.4176127l
-2.29hOlZbl
1050*l15l
1.35281?31
2.35q31151
0.59047llRl
2, P C 6 0 1 ? Z l 0.28751271
-2.26?8l151
c.
0.258551191
0.73k991171
0.168241161 -0.07473I15l
2 , 539 I i i a
0,155 9 I24I 0.8906l27l
- 1.624Ef321 i
2.1758tZZI
-0.1331 ( 3 2 1
2.0 a 8 5 ( 1 7 1
3.0209(18l
-3.1941 1 191
3.15911191
3.05441171
-l12b75IPl I
2.5235 (241
C ,6662 ( 3 3 1
.........**.....*....*......**...*~.*....*.... '*....,..*............................**.................*..... 0.17129 (221
pnn
0.33567 I251
2.3802IZZl
1.27471291
0 . 7 6 7 5 12 7 I
*
.1.................
AX
c
V
c
t
AN0 2
ARE THE F R A C T I O N A L C O O Q O I N A T E S OF
S I L O N . AN0 E T 4 ( R A O I A N S I
THC O R I G I N
HAVE BEEN D E F I N E D P R E V I O O S L Y :
S.J.
OF THE
PIGIO
R I G I D G R O U P . 'THE
LA PLACA AN0 J . A .
[EERS,
GROlJP O R I E h T A T I D N ANGLES D E L T A ,
ACTA C S I S T A L L O G R . ,
18,
IP-
511l19651,
Table VI. Interatomic Distances (A) and Angles (deg) in trans-[RuH(dtt)(CO)(PPh,), ] Ru-P(1) Ru-P(2) Ru-N(1) Ru-N( 3) Ru-C( 1) Ru-C(2)= P( 1)-PH3C1 P( 1)-PH4C1 P( 1)-pH5 C 1 P(2)-PH6Cl Ru-N(2) Ru-O(l)
Figure 2. Overall view of the trans-[Ru(H)(dtt)(CO)(PPh,),l complex. In this and the follgwing drawing the 20% disordered carbonyl is not shown for clarity but the H atom is placed at the position of C(2). Both figures show the atoms at the 50% probability contour of thermal motion.
P( l)-Ru-P(2) P( l)-Ru-N(l) P(l)-Ru-N( 3) P( l)-Ru-C( 1) P( l)-Ru-C(2) P(2)-Ru-N( 1) P(2)-Ru-N(3) P(2)-Ru-C( 1) P(2)-Ru-C(2), N( l)-Ru-N(3) N(l)-Ru-C(l) N(l)-Ru-C(2) N(3)-RuC( 1) N(3)-Ru-C(2) C(l)-Ru-C(2) Ru-P( l)-PH 3C 1 Ru-P( 1)-PH4C1 Ru-P( l)-PHSCl
Bonding Distances 2.343 (1) P(2)-PH7C1 2.354 (1) P(2)-PH8C1 2.149 (3) N(l)-PHlCl 2.179 (3) N(3)-PH2Cl 1.866 ( 5 ) N(l)-N(2) 1.80 (2) N(2)-N(3) 1.836 (3) C(1)-0(1) 1.840 (3) C(2)-0(2)' 1.830 (3) C(3)-PHlC4 1.833 (2) C(4)-PH2C4 Nonbonding Distances 2.694 (3) Ru-0(2) N(l)-N(3) 3.026 (4) Bond 173.44 (3) 90.87 (8) 94.35 (8) 89.8 (1) 84.5 ( 6 ) 93.23 (8) 9 2.17 (8) 87.6 (1) 90.0 (6) 57.7 (1) 165.2 (2) 95.1 ( 6 ) 107.5 (2) 152.7 (6) 99.7 (6) 116.9 (1) 115.9 (1) 114.8 (1)
1.838 (3) 1.814 (2) 1.408 (3) 1.411 (3) 1.318 (4) 1.310 (4) 1.161 (6) 1.18 (3) 1.525 (6) 1.523 (5) 2.97 (2) 2.087 (4)
Angles PH3Cl-P(l)-PH4%1 PH3Cl-P(l)-PHSCl PH4Cl-P(l)-PHSCl Ru-P(2)-PH6Cl Ru-P(2)-PH7Cl Ru-P(2)-PH8Cl PH6C 1-P(2)-PH7C 1 PH6Cl-P(2)-PH8Cl PH7Cl-P(2)-PH8Cl Ru-N(l)-N(2) Ru-N(l)-PhlCl PHlCl-N(l)-N(2) N(l)-N(2)-N(3) Ru-N(3)-N(2) Ru-N(3)-PH2Cl PH2Cl-N(3)-N(2) RuC(l)-O(l) Ru-C(2)-0(2)
100.9 (1) 101.3 (1) 104.9 (1) 118.6 (1) 118.0 (1) 111.0 (1) 100.7 (1) 104.2 (1) 102.3 (2) 99.2 (2) 145.1 (2) 115.5 (2) 105.2 (3) 98.0 (2) 145.6 (2) 116.1 (2) 178.5 (5) 177 (2)
'
C(2) and O(2) are the minor components of the disordered carbonyl group.
Figure 3. View of the coordination geometry about the ruthenium atom.
The minor positional disorder in the structure, as mentioned in the previous section, consists of a partial carbonyl occvpancy in the hydride position. As determined from the least-squares refinement the occupancy factor is 0.198 (5) for C(2)-0(2) and 0.802 (5) for C( 1)-O( 1). The contribution of the hydrido ligand was not taken into account, but the electron density distribution suggests that the hydride position is very close to that of atom C(2). Accordingly, we display the H ligand at the position of C(2) and omit C(2) and O(2) from the drawings. The bond distances and angles of C(2)-0(2), as shown in Table VI, are acceptable for a carbonyl group when the telatively large standard deviations are taken into account. The type of disorder observed in this structure is not unusual as a number of structures showing a positional disorder between a halide and carbonyl have been r e ~ o r t e d . ~ ' -A~ ~ 50%-50% (Le,, statistical) disorder is not always found as
shown in the structure reported here and in at least one other structuree29 The most interesting feature of the present structure involves the ruthenium-triazenido system. There is a small, possibly significant, difference in the Ru-N( 1) and Ru-N(3) bond lengths (2.149 (3) and 2.179 (3) A, respectively) owing perhaps to the trans influence of the hydrido ligand which is mainly opposite to atom N(3). The N(l)-N(Z)-N(3) angle of 105.2 (3)' is much smaller than the typical 117' angle observed in structures having a triazenido ligand bridging two metal center^.^-^ That there is extensive a delocalization over the ruthenium-triazenido system is apparent from the equivalence of the two N-N bond lengths (average of 1.314 (4) A, intermediate between a single- and a double-bond distance) and from the near planarity of the entire system. This planarity can readily be seen in Figure 2 and from the data of Table VII, where various least-squares planes are presented. The angle between the two tolyl rings is 15.4', whereas the angles
,
I
between the planar Ru-N(1)-N(2)-N(3) ring and each of the two tolyl rings PHI and PH2 are 18.1 and 5.6', re-
2792 Inorganic Chemistry, Vol. 15, No. 11, 1976
Leo D. Brown and James A. Ibers
Table VII. Selected Weighted Least-Squares Planes Coefficients of the Plane Equation A x Plane
A
B
1 2 3 4 5 6b 7c
12.560 12.571 12.464 12.504 12.559 11.302 12.848
11.164 10.971 10.981 10.994 11.129 9.354 10.122
+ B y + Cz = Da D
C -7.474 -7.669 -7.866 -7.780 -7.519 -10.048 -7.856
2.205 2.096 2.006 2.039 2.185 1.102 2.127
Deviations (A) of Various Atoms from the Planes Atom
N(3j C(1)
Plane 1
Plane 2
Plane 3
Plane 4
Plane 5
-0.0006 (4)d 0.012 (1) -0.013 (1) 0.006 (1)
-0.0074 (4) 0.028 (1) 0.034 (1) 0.054 (1)
-0.0159 (4) 0.065 (1) 0.083 (1) 0.079 (1)
-0.0054 (4) 0.013 (1) -0.006 (1) 0.013 (1) -0.001 (1) 0.011 (1) 0.011 (1) 0.047 (4)
-0.343 -0.500 -0.046 -0.461 -0.558 -0.239 0.176 0.272 -0.078 -0.144 -0.280 -0.352 -0.286 -0.149
-0.354 (4) -0.328 (4) -0.036 -0.426 -0.5 30 -0.243 0.147 0.251 0.000 -0.065 -0.172 -0.213 -0.147 -0.041
-0.237 (4) -0.281 (4) 0.021 (4) -0.340 (4) -0.424 (3) -0.147 (4) 0.214 (4) 0.298 (3) 0.033 (7) -0.057 (7) -0.159 (6) -0.171 (6) -0.082 (6) 0.020 (5)
-0.0028 (4) 0.060 (1) 0.071 (1) 0.076 (1) -0.026 (1) -0.031 (1) -0.025 (1) -0.013 (4) -0.270 (4) -0.302 (4) 0.009 (4) -0.365 (4) -0.456 (3) -0.173 (4) 0.201 (4) 0.292 (3) 0.024 (7) -0.057 (7) -0.163 (6) -0.188 (6) -0.107 ( 6 ) -0.001 (5)
oiij C(2) O(2) C( 3) (34) PHlCl PHlC2 PHlC3 PHlC4 PHlC5 PHlC6 PH2C1 PH2C2 PH2C3 PH2C4 PH2C5 PH2C6
Dihedral Angles between Planes Plane A
Plane B
Angle, deg
Plane A
1 1 1 1 1 1
2 3 4 5 6 7 3 4 5 6 7
1.43 2.42 1.92 0.30 18.14 5.62 1.25 0.73 1.13 16.84 4.42
3 3 3 3 4 4 4 5 5 6
2 2 2 2 2
a The plane is in crystal coordinates. Plane of phenyl 1. Plane of phenyl 2. parentheses indicate the atoms which determined each of the least-squares planes.
spectively. In the structures of Co(dpt)3, these interplanar angles range from 5.2 to 31.1' for the unsolvated forms and are approximately 20' in the toluene solvated form.6 The structures of two ruthenium complexes containing bidentate acetate and formate ligands (isoelectronic with triazenido) merit comparison with the ruthenium triazenido complex reported here. These compounds are RuH(02CMe)(PPh3)325 and R U H ( O ~ C H ) ( P P ~The ~ ) ~car.~~ boxylate groups in both of these structures have equivalent C-0 bond lengths indicative of the expected r-delocalized system. The small 0-Ru-0 bite angles of 57.6 (4) and 55.0 (13)' for the acetate and formate structures, respectively, agree very well with the N( 1)-Ru-N(3) angle of 57.7 (1)' found in the triazenide. The 0-C-0 angles in the acetate and formate complexes are larger (1 14.8 and 114.2', respectively) than the 105.2" triazenide N( l)-N(2)-N(3) angle. This difference reflects the longer Ru-0 and the shorter C-0 bond distances (ca. 2.20 and 1.25 A, respectively) in the carboxylate structures compared with the Ru-N and N-N bonds in the triazenide. Within the rather large standard deviations in both the acetate and formate structures the trans influence of the
Plane B
Angle, deg
6 7 7
0.54 2.14 15.72 4.57 1.63 16.23 4.55 17.85 5.38 15.38
Numbers with estimated standard deviations given in
hydrido ligand was not detected. Skapski and Stephens25 indicated that the RuH(02CMe)(PPh3)3 complex may be considered to be pseudo five-coordinate with the center of the bidentate group taken as a fifth coordination site. In this context the present ruthenium triazenide structure is a pseudo trigonal bipyramid with the trans triphenylphosphine groups in the axial positions and with equatorial angles N(2)Ru-C(l) = 136.3 (2)', N(2)-Ru-C(2) = 123.9 (6)', and C(l)-Ru-C(2) = 99.7 (6)'. This type of geometric interpretation has also been discussed elsewhere.26 Very recently, the structure of another bidentate triazenido complex, Mo(dfpt)(CsH5)(CO)2 (dfpt = 1,3-bis(3,5-bis(trifluoromethyl)phenyl)triazenido), was reported.31 The important distances and angles found in this Mo triazenide structure, the two Co(dpt)3 structure^,^^^ and the ruthenium triazenide structure reported here are compared in Table VIII. The N-N and N-C distances agree very well for all four structures. The small N-N-N angles are evidence of the strain in the four-membered M-N-N-N ring. Among these angles, there is very close agreement between the two Co(dpt)3
-
Inorganic Chemistry, Vol. 15, No. 11, 1976 2793
Triazenido Complexes Table VIII. Structural Parameters for Reported Bidentate Triazenido Complexes [Co(d~t),l. C, H,CH,a Co(dpt) M-N. A
1.93 (1)
1.919 ( 5 )
N-N, A N-N-N, N-M-N, M-N-N, N-C, A M-N-C, N-NC,
[Mo(dfpt)- trans-[RuH(CsHs)- (dtt)(CO)(CO), 1' (PPh,) ,Id 2.120 (9)
2.149 (3) 2.179 (3) 1.314 (4) 105.2 (3) 57.7 (1) 98.6 (2) 1.410 (3) 145.4 (2) 115.8 (2)
1.32 (1) 1.311 (7) 1.31 (1) deg 103.6 (7) 103.2 (7) 100.8 (7) deg 65.5 (5) 64.8 (3) 56.8 (3) deg 95.5 (6) 96.0 (4) 1.40 (1) 1.407 (7) 1.423 (13) deg 144.9 (6) deg 118.4 (6) 118.9 (5) 116.5 (8) a Reference 7. Reference 8. Reference 31. This work.
'
structures; their average value is about 2" less than in the Ru structure. This difference can be accounted for by the smaller size of the Co compared with the Ru atom. In the Mo structure, however, this N-N-N angle is further reduced to 100.8 (7)", almost '5 less than for the Ru complex. Since the Mo(I1) bonding radius is comparable with that of Ru(II), the change in N-N-N angle must result from the vastly different ligand environments of the two complexes. The N-M-N angles in the Mo and Ru complexes (56.8 (3) and 57.7 (I)", respectively) are much smaller than that of about 65" in the Co(dpt)3 complexes. This is expected upon consideration of the longer metal-nitrogen distance in the Mo and Ru complexes. Based upon a simple geometric relation (sin [(N-M-N)/2] a M-N distance) and the given M-N distances, a N(l)-Ru-N(3) angle of 57" results from the N-Co-N angle of 65". Acknowledgment. We are indebted to Dr. S . D. Robinson for supplying the original sample of the ruthenium complex. This work was supported by the National Science Foundation. Registry No. truns-Ru(H)(dtt)(CO)(PPh3)2,54206-37-0. Supplementary Material Available: Table IV, the root-mean-square amplitudes of vibration, Table V, a listing of the idealized positions of the hydrogen atoms, and a listing of observed and calculated structure amplitudes (43 pages). Ordering information is given on any current masthead page.
References and Notes (1) F. P. Dwyer and D. P Mellor, J Am. Chem SOC,63, 81 (1941). (2) C. M. Harris, B. F. Hoskins, and R. L. Martin, J . Chem Soc., 3728 ( 1959).
(3) M. Corbett and B. F. Hoskins, Chem. Commun., 1602 (1968). (4) M. Corbett, B. F. Hoskins, N. J. McLeod, and B. P. O'Day, Aust. J . Chem., 28, 2377 (1975). I. D. Brown and J. D. Dunitz, Acta Crystallogr., 14, 480 (1961). M. Corbett and B. F. Hoskins, J . Am. Chem. Soc., 89, 1530 (1967). M. Corbett and B. F. Hoskins, Aust. J. Chem., 27, 665 (1974). W. R. Krigbaum and B. Rubin, Acta Crystallogr., Sect. B, 29,749 (1973). (a) K. R. Laing, S. D. Robinson,and M. F. Uttley, J. Chem. Soc., Dalton Trans., 1205 (1974); (b) S. D. Robinson and M. F. Uttley, Chem. Commun., 1315 (1971); (c) S. D. Robinson and M. F. Uttley, J . Chem. Soc., Chem. Commun., 184 (1972). W. H. Knoth, Inorg. Chem., 12, 38 (1973). J. Kuyper, P. I. van Vliet, and K. Vrieze, J. Organomet. Chem., 96, 289 (1975). E. Pfeiffer, J. Kuyper, and K. Vrieze, J . Organomet. Chem., 105, 371 (1976). J. Kuyper, P. I. van Vliet, and K. Vrieze, J . Organomet. Chem., 105, 379 (1976). R. B. King and K. C. Nainan, Inorg. Chem., 14, 271 (1975).
L. Toniolo, G. De Luca, and C. Panattoni, Synth. Inorg. Met.-Org. Chem., 3, 221 (1973). S. C. De Sanctis, L. Toniolo, T. Boschi, and G. Deganello, Inora. Chim. Acta, 12, 251 (1975). (17) S. C. DeSanctis, N. V. Pavel, and L. Toniolo. J . Oraanomet. Chem.. 108, 409 (1976). (18) A preliminary report of this structure has appeared: L. D. Brown and J. A. Ibers, J . Am. Chem. Soc., 98, 1597 (1976). (19) R. J. Doedens and J. A. Ibers, Inorg. Chem., 6, 204 (1967). (20) In addition to various local programs for the CDC 6400 computer,
programs used in this work include local versions of Zalkin's FORDAP Fourier program, Busing and Levy's ORFFE function and error program, and the AGNOST absorption program (which includes the CoppensLeiserowitz-Rabinovich logic for Gaussian integration). Our full-matrix least-squares program NUCLS, in its nongroup form, closely resembles the Busing-Levy ORFLS program. A special modification, NUCLS5H, was used on the Lawrence Berkeley Laboratory CDC 7600 computer for refining anisotropic groups. The diffractometer was run under the Vanderbilt Disc System as described by P. G. Lenhert, J . Appl.
Crystallogr., 8, 568 (1975). (21) D. T. Cromer and J. T, Waber, "International Tables for X-Ray Crystallography", Vol. IV, Kynoch Press, Birmingham, England, 1974, Table 2 . 2 4 D. T. Cromer and D. Liberman, J . Chem. Phys., 53, 1891 (1970). (22) S. J. La Placa and J. A. Ibers, Acta Crystallogr., 18, 511 (1965). (23) K. N. Raymond, Acta Crystallogr., Sect. A, 28, 163 (1972). (24) Supplementary material. (25) A. C. Skapski and F. A. Stephens, J. Chem. SOC.,Dalton Trans., 390 (1 974). (26) S. Komiya, T. Ito, M. Cowie, A. Yamamoto, and J. A. Ibers, J . Am. Chem. Soc., 98, 3874 (1976). (27) S. J. La Placa and J. A. Ibers, J . Am. Chem. Soc., 87, 2581 (1965). (28) J. A. McGinnety, R. J. Doedens, and J. A. Ibers, Science, 155,709 (1967). (29) S. Z. Goldberg, E. N. Duesler, and K. N. Raymond, Inorg. Chem., 11, 1397 (1972). (30) (a) I. S. Kolomnikov, A. I. Gusev, G. G. Aleksandrov, T. S. Lobeeva, Yu.T. Struchkov, and M. E. Vol'pin, J . Organomet. Chem., 59, 349 (1973); (b) A. I. Gusev, G. G. Aleksandrov, and Yu. T. Struchkov. J . Struct. Chem., 14, 633 (1973). (31) E. Pfeiffer and K. Olie. Cryst. Struct. Commun., 4, 605 (1975)
